Polyols derived from a vegetable oil using an oxidation process

ABSTRACT

A method for producing a vegetable oil-derived polyol having increased hydroxyl functionality by reacting a vegetable oil with an oxidizing agent in the presence of an organometallic catalyst is provided. The resulting higher functionality polyols derived from vegetable oil produced by the process are also provided. Also provided is a method for decreasing the acid value of a vegetable oil-derived polyol by reacting the vegetable oil-derived polyol with an epoxide component in the presence of a Lewis base catalyst. Urethane products produced using higher functional vegetable oil-derived polyols and/or lower acid vegetable oil-derived polyols are also provided.

CROSS REFERENCE TO RELATED APPLICATION

This application is a Divisional of application Ser. No. 11/368,159, nowU.S. Pat. No. 7,989,647, entitled NOVEL POLYOLS DERIVED FROM A VEGETABLEOIL USING AN OXIDATION PROCESS, filed on Mar. 3, 2006, the disclosure ofwhich is hereby incorporated by reference in its entirety. U.S.application Ser. No. 11/368,159 claims priority to and the benefit ofU.S. Provisional Application Ser. No. 60/658,230, filed on Mar. 3, 2005,entitled NOVEL POLYOLS DERIVED FROM A VEGETABLE OIL USING AN OXIDATIONPROCESS, the disclosure of which is hereby incorporated by reference inits entirety.

BACKGROUND OF THE INVENTION

Because of their widely ranging mechanical properties and their abilityto be relatively easily machined and formed, polyurethane materials,such as urethane elastomers and foams, have found wide use in amultitude of industrial and consumer applications.

The production of urethane polymers is well known in the art. Urethanesare formed when isocyanate (NCO) groups react with hydroxyl (OH) groups.The most common method of urethane production is via the reaction of apetroleum-derived polyol and an isocyanate, which forms the backboneurethane group. Polyester polyols and polyether polyols are the mostcommon polyols derived from petroleum used in urethane production.Polyols are polyhydric alcohols, i.e., alcohols that contain two or morehydroxyl groups.

Sole use of polyols derived from petrochemicals such as polyester orpolyether polyols in forming urethane products such as elastomers andfoams is disadvantageous for a variety of reasons. Petrochemicals areultimately derived from petroleum. Accordingly, the petrochemicals are anon-renewable resource. The production of a petroleum-derived polyolrequires a great deal of energy, as oil must be drilled, extracted fromthe ground, transported to refineries, refined, and otherwise processedto yield the polyol. These efforts add to the cost of polyols and to thedisadvantageous environmental effects of its production. Also, the priceof petroleum-derived polyols tends to be somewhat unpredictable as ittends to fluctuate based on the fluctuating price of petroleum.

Also, as the consuming public becomes increasingly aware ofenvironmental issues, there are distinct marketing disadvantages topetrochemical based products. Consumer demand for “greener” productscontinues to grow. As a result, it would be most advantageous to replaceall or at least some of the polyester or polyether polyols, as used inthe production of urethane polymers, with a more versatile, renewable,less costly, and more environmentally friendly component, such asvegetable oil-derived polyols.

One difficulty with the use of vegetable oil-derived polyols to producea urethane product is that conventional methods of preparing polyolsfrom vegetable oils, such as soybean oils, do not produce polyols havinga significant content of hydroxyl groups. Accordingly, it would beadvantageous to develop a method to produce vegetable oil-based polyolshaving increased reactive hydroxyl groups over conventional polyolsderived from a vegetable oil such as blown vegetable oil.

Another difficulty with the use of vegetable oil-derived polyols toproduce a urethane product is higher than desired residual acid valuesof the polyol, especially in blown soybean oil polyols (typical blownsoybean oil-derived polyol, the residual acid value of a soybeanoil-derived polyol ranges from about 5.4 mg KOH/gram to about 7.4 mgKOH/gram). Generally, in the production of urethane elastomers andfoams, the residual acid present in vegetable oil-derived polyolsretards isocyanate activity by interfering with the isocyanate/alcoholreaction. Also, where the catalyst used to produce urethane polymers isan amine, it is believed that the residual acid can neutralize theamine, making the catalyst less effective. Accordingly, it would beadvantageous to develop a method to neutralize the residual acid of thepolyol to form reactive hydroxy (OH) groups while not adverselyimpacting performance of the polyol. A lower acid vegetable oil-derivedpolyol would be desirable because the lower acid value would improve theperformance of polyols in the production of urethane polymer, lowerpolyurethane catalyst requirements, and improve urethane physicalproperties due to improved polymer network formation. Accordingly, asignificant need exists for low acid, higher functional polyols derivedfrom vegetable oil, especially polyols derived from soybean oil,typically blown soybean oil, and a method for producing such lower acid,higher functional polyols.

BRIEF SUMMARY OF THE INVENTION

One embodiment of the present invention generally relates to a methodfor making polyols derived from vegetable oil where the polyols haveincreased hydroxyl functionality where a vegetable oil, typicallysoybean oil, is reacted with an oxidizing agent in the presence of anorganometallic catalyst and the resulting higher functional polyolsderived from vegetable oil produced by the process.

Another embodiment of the present invention generally relates to loweracid, higher functionality polyols derived from a vegetable oil and anew method for decreasing the acid value of a polyol by reacting avegetable oil-derived polyol having increased functionality formed byreacting the vegetable oil, typically a blown soybean oil, with anoxidizing agent in the presence of an organometallic (tetra amidomacrocylic ligand) catalyst with an epoxide component in the presence ofa Lewis base catalyst.

The present invention further generally relates to the use of (1) thehigher functional polyol derived from a vegetable oil, typically arefined and bleached vegetable oil, formed by reacting an oxidizingagent with the vegetable oil in the presence of an organometalliccatalyst and/or (2) the lower acid, higher functional vegetableoil-derived polyols as the polyol or one of various polyols and/or as acomponent of a prepolymer in the production of urethane material,including foams and elastomers. The polyols may be one of the componentsof the B-side, which can be reacted with an A-side that typicallyincludes a prepolymer (traditional petroleum-derived prepolymer or aprepolymer incorporating a polyol at least partially derived from avegetable including a lower acid vegetable oil-derived polyol) or anisocyanate.

Another embodiment of the present invention includes the use of thehigher functional, typically also lower acid polyols derived fromvegetable oil as one of the B-side components (other polyols derivedfrom petroleum may also be used in combination with the higherfunctional polyols of the present invention as polyol components of theB-side) that is reacted with an A-side that includes an isocyanateand/or a prepolymer, such as the prepolymers discussed above, to form aurethane material. The urethane materials can be used as a precoat andfor a backing material for carpet, building composites, insulation,spray foam insulation, other urethane applications such as thoserequiring use of impingement mix spray guns, urethane/urea hybridelastomers, vehicle bed liners, flexible foams (furniture foams, vehiclecomponent foams), integral skin foams, rigid spray foams, rigidpour-in-place foams, coatings, adhesives, sealants, filament winding,and other urethane composites, foams, elastomers, resins, and reactioninjection molding (RIM) applications.

These and other features, advantages, and objects of the presentinvention will be further understood and appreciated by those skilled inthe art by reference to the following specification, claims, andappended drawings.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENT

Applicant has surprisingly discovered that oxidation of a vegetable oil,most typically soybean oil, in the presence of an organometalliccatalyst, typically a TAML® (tetra amido macrocyclic ligand) catalyst,results in a vegetable oil-derived polyol having increased hydroxylgroup functionality. A method for producing vegetable oil-derivedpolyols with increased functionality having lower acid values has alsobeen developed.

The method for making a vegetable oil-based polyol with increasedfunctionality generally includes reacting a vegetable oil, typicallysoybean oil, more typically a refined, bleached soybean oil, with anoxidizing agent in the presence of an organometallic (tetra amidomacrocyclic ligand) oxidation catalyst. Generally, the oxidationreaction occurs at elevated temperatures of from about 95° C. to about150° C., more typically from about 95° C. to about 110° C., and mosttypically about 95° C. However, it is presently believed that theoxidation reaction may function at temperatures of about 50° C. orgreater. This oxidation process yields a polyol with a hydroxyl valueranging from about 56 mg KOH/gram polyol to about 220 mg KOH/grampolyol. More typically, this oxidation process yields a polyol with ahydroxyl value ranging from about 112 mg KOH/gram of polyol to about 220mg KOH/gram polyol.

Oxidation Reaction

In the oxidation reaction of one embodiment of the present invention,the oxidizing agent is typically a chemical which can act as an electronreceptor or is a substance in an oxidation-reduction reaction that gainselectrons and whose oxidation number is reduced. Typically, hydrogenperoxide or air and most typically hydrogen peroxide is utilized.However, it is presently believed that oxidizing agents can include allorganic peroxides. Typically, where the oxidizing agent is air, driedair is preferably introduced at a rate of about 300 cubic feet perminute (CFM) for the volume of oil used. Where the oxidizing agent ishydrogen peroxide, a solution of from about 35% to about 50% hydrogenperoxide is preferably used. A higher concentration of hydrogen peroxideis generally preferred in order to maximize contribution to the reactionof the oxidizing agent and for completion of the reaction. Preferably,the hydrogen peroxide solution is utilized in amounts ranging from about10% by weight to about 50% by weight of the reaction material.

Typically, the polyol is a polyol at least partially derived from avegetable oil, typically a soybean oil, a rapeseed oil, a palm oil, asafflower oil, a sunflower oil, a corn oil, a linseed oil, a tall oil, atoung oil, a canola oil, or a cottonseed oil, more typically a refined,bleached soybean oil, and most typically a refined, bleached soybean oilproduced according to the process disclosed in U.S. Pat. Nos. 6,476,244and 6,759,542, the disclosures of which are incorporated by reference intheir entirety.

The vegetable oil-derived polyol, typically a polyol derived fromsoybean oil, is oxidized in the presence of an organometallic catalyst,typically a TAML® (tetra amido macrocyclic ligand) catalyst, mosttypically Fe-TAML® (iron tetra amido macrocyclic ligand) catalyst. Tetraamido macrocyclic ligand is an environmentally friendly catalyst thatcauses an oxygen component to work faster and more safely. Specifically,where the oxidizing agent is hydrogen peroxide, the tetra amidomacrocyclic ligand catalyst forms activated peroxides that are veryreactive, but more selective than free radicals formed during the normaldecomposition of hydrogen peroxide. The structure of a tetra amidomacrocyclic ligand catalyst is shown below. It is currently believedthat an inorganic metal tetra amido macrocyclic ligand activatedperoxide complex, typically one based on an iron tetra amido macrocyclicligand, associates with double bonds on the soybean oil to form hydroxylgroups at the available vinylic sites of the vegetable oil. In theoxidation reaction of one embodiment of the present invention, theamount of the tetra amido macrocyclic ligand catalyst used is typicallyfrom about 0.2 ppm to about 200 ppm of catalyst used in the reaction,preferably from about 0.2 to about 2.0 ppm, and most preferably about0.2. However, it is presently believed that the amount of tetra amidomacrocyclic ligand catalyst may be 0.01 ppm or greater.

Applicants have surprisingly discovered that oxidizing a vegetable oil,most typically a soybean oil, in the presence of an organometalliccatalyst, typically a tetra amido macrocyclic ligand catalyst, mosttypically an Fe— (tetra amido macrocyclic ligand catalyst), results in avegetable oil-derived polyol having increased hydroxyl groupfunctionality of about 56 mg KOH/gram polyol to about 220 mg KOH/grampolyol, more typically of greater than 85 mg KOH/gram polyol as comparedto vegetable oil oxidized by blowing processes, which typically yields apolyol with a hydroxyl value ranging from about 56 mg KOH/gram polyol toabout 80 mg KOH/gram polyol.

The following examples demonstrate the oxidation of a vegetable oil,typically soybean oil, in the presence of a tetra amido macrocyclicligand catalyst to form a vegetable oil-derived polyol having increasedhydroxyl functionality.

The following general experimental procedure and sample analysis wasused for all example oxidation reactions discussed below. In amulti-neck reactor flask equipped with an agitator blade on a stir shaftconnected to a stir motor, a quantity of refined, bleached soybean oilwas heated. One neck of the flask was equipped with a 300 mm vigreauxcolumn packed with glass beads beneath a water-cooled side-arm condenserso that distillate could be collected and vacuum distillation could beperformed at the end of reaction if desired. A temperature probe andnitrogen inlet were present in the flask. The soybean oil was heated toa desired reaction temperature, typically a temperature of from about95° C. to about 130° C., before adding the tetra amido macrocyclicligand catalyst. In air oxidation experiments, dried air wasincorporated into the reaction mixture through a stainless steel spargertube at a rate equivalent to 300 cubic feet per minute for the volume ofoil used. In hydrogen peroxide oxidation experiments, the peroxidesolution was added in increments specified in each reaction.

Periodic samples were removed from the flask while the reaction mixturewas stirred. To indicate the presence or absence of peroxide in thereaction mixture samples, sodium bisulfite was added to the sample. Ifperoxides are present, they react with the bisulfite to generate SO₂ gasin a vigorous, bubbling, exothermic reaction. Even a mild reactionbetween bisulfite and peroxide can be detected by suspending a strip ofpH paper above a beaker containing the reactants (pH paper turns red inthe presence of the acidic gas). Bisulfite was effective in neutralizingperoxides in reaction samples; however, the presence of bisulfiteinterfered in hydroxyl titrations. When possible, samples were analyzedbefore adding large quantities of peroxide to minimize the effect ofperoxides and moisture on titrations. Samples containing considerablequantities of water were allowed to phase separate before analyzing theoil/polyol fraction.

Titrimetric analytical methods were used to track reaction progress inthese reactions. Analytical methods include hydroxyl titration (ASTM D4274-99, B), acid value titration (ASTM D 4662-03, A), and viscosity(ASTM D 4878-03, A).

The following oxidation reactions were conducted using 300 CFM (cubicfeet per minute) dried air for the volume of oil used.

TABLE 1 Experiment No. 1 2 3 Weight soybean oil (grams) 502.62 506.31500 TAML ® concentration (ppm) 100 100 50 Temperature (° C.) 115 115 115Total reaction time (hours) 42 27 35 Final viscosity (cPs) 20636 22577693 Final acid value (mg KOH/gram sample) 11.31 7.9 8.82 Finalcorrected hydroxyl value (mg KOH/ 65.9 64.9 71.47 gram sample)

The following oxidation reactions were carried out using hydrogenperoxide as the oxygen component.

TABLE 2 Experiment No. 1 2 3 4 5 6 Weight soybean 500 500 515.8 500 500800 oil (grams) TAML ® con- 50 50 5 5 5 1 centration (ppm) Hydrogenperox- 50 50 35 50 50 50 ide concen- tration (%) Weight of 338.56 388.56496.6 347.6 347.6 556.2 hydrogen peroxide (grams) Temperature 110 110110 110 130 110 (° C.) Total reaction 20 96 140 81 — 64 time (hours)Final acid value 1.13 24.21 — 3.86* — 1.16* (mg KOH/gram sample) Finalcorrected 10.26 127.04 67.23 172.12* — 143.3* hydroxyl value *Final acidvalues and final corrected hydroxyl values were measured after theresulting vegetable oil-derived polyol was subjected to the residualacid reduction method described below.Residual Acid Value Reduction

One potential drawback of using the tetra amido macrocyclic ligandcatalyst process described above to form highly functionalized polyolsderived from vegetable oil is the fact that the process tends to producea polyol with high residual acid values. High residual acid values inpolyols are undesirable in most all applications because the acidsinhibit catalysts and urethane reaction rates. Applicants havediscovered that a higher residual acid value, high functionality polyolis well suited for use as a replacement for some (or all) of the polyolsderived from petroleum when urethanes are used in applications, longerpot life reactions yield better products and provide greater processingflexibility. However, for a majority of urethane applications, theresidual acid values are undesired. Accordingly, Applicants havediscovered a process to lower the residual acid value of the higherfunctional polyols.

A vegetable oil-derived polyol of one embodiment of the presentinvention formed by oxidation of a vegetable oil, typically soybean oil,in the presence of an organometallic catalyst, typically a TAML®catalyst, may further be reacted with an epoxide component to reduce theamount of residual acid present in the polyol. As used herein, the “acidvalue” of an acid-functional polyol is a measurement of the amount ofbase, typically sodium hydroxide (NaOH), necessary to neutralize theresidual acid present in the polyol. It is presently believed that theresidual acid is the result of either decomposition of triglycerideester bonds into free fatty acids or oxidizing alcohols into carboxylicacids. The acid value is determined by weighing a small sample,typically from less than one gram to about 10 grams, more typically fromabout 2 to about 10 grams, of the polyol into a flask. A solvent,typically acetone or a mixture of acetone and isopropyl alcohol in a 1:1ratio, is added to the flask to dissolve the polyol. The solution istitrated with a standardized solution of sodium hydroxide (NaOH) andreported in units of milligrams KOH per gram of sample. The acid valueof a typical blown soybean-derived polyol typically ranges from about5.4 mg KOH/gram to about 7.4 mg KOH/gram.

The polyol derived from vegetable oil or a polyol derived from a blownsoybean oil polyol, which may or may not have been reacted with thetetra amido macrocyclic ligand catalyst as described above, is reactedwith an epoxide component. An epoxide is an organic group containing areactive group characterized by the union of an oxygen atom with twoother atoms, typically carbon, to form:

wherein R is either H or an organic group.

In this embodiment of the present invention, any epoxide can be reactedwith a polyol derived from vegetable oil. Typically, the epoxideutilized is neodecanoic acid 2,3-epoxypropylester. Other epoxides thatmay be utilized include polyglycol di-epoxides such as D.E.R.™ 736available from Dow Chemical of Midland, Mich., and glycidyl esters andglycidyl epoxy ether such as CARDURA™ E10P, available from ResolutionPerformance Products of Houston, Tex. Alternatively, a mixture ofepoxides may be used in this embodiment of the present invention. Theamount of epoxide used in the reaction typically ranges from about 90%to about 500% of the stoichiometric molar amount of acid in carboxylicgroups present in the vegetable oil-derived polyol.

The vegetable oil-derived polyol and the epoxide are typically reactedin the presence of a Lewis base catalyst or mixture of Lewis basecatalysts. The Lewis base catalyst used to neutralize residual acid inthe polyols derived from vegetable oil, typically blown soybean oilpolyol, in this embodiment of the present invention are Lewis basecatalysts that are generally known in the art. Examples of Lewis basecatalyst that may be used include: tertiary amines such as DABCO 33-LV®comprised of 33% 1,4-diaza-bicyclo-octane (triethylenediamine) and 67%dipropyleneglycol, a gel catalyst available from the Air ProductsCorporation of Allentown, Pa.; DABCO® BL-22, a tertiary amine alsoavailable from the Air Products Corporation; POLYCAT® 41 trimerizationcatalyst (N,N′,N″-dimethylaminopropylhexahydrotriazine) available fromthe Air Products Corporation; and Air Products DBU® (1,8 diazabicyclo[5.4.0]). Dimethylethanolamine (DMEA) and triphenyiphosphine (TPP) mayalso be used as the Lewis base catalyst. Other catalysts that can beused in the present invention include such compounds as the amines,mono-, di- and tri-aliphatic and alkanol amines, pyridines, piperidines,aromatic amines, ammonia, ureas, quinolines, imidazoles and imidazolinesand other heterocyclic nitrogen compounds and the like. Examples includeaniline, triethylene diamine, imidazole, piperidine, pyrrolidine anddiethanolamine. Another class of such Lewis base catalysts areorganometallic compounds such as dibutyl tin oxide, monobutyl tinchloride, triphenyl phosphine and other organometallic compounds withunshared electron pairs such as metal carbonyls and phosphine orphosphite complexes, e.g. iron pentacarbonyl. Especially preferred arethe organo-tin Lewis base catalysts, more specifically dibutyl tin oxideand monobutyl tin chloride, and the N-substituted tetra(lower alkyl)ureas, more specifically N,N,N′,N′ -tetramethyl urea.

The Lewis base catalysts used to produce lower acid vegetableoil-derived polyols are also catalysts in the preparation of urethanes,so it may be acceptable to use an amount in excess of what is necessaryfor the polyol-epoxide reaction. However, too great an excess of Lewisbase catalyst is not preferred because too much Lewis base catalyst maynegatively affect the color, odor, and viscosity of the resultingpolyol. In one embodiment of the present invention, the Lewis basecatalyst is typically present in an amount of from about 0.1 weightpercent to about 0.3 weight percent relative to epoxide content used inthe reaction.

The polyol-epoxide reaction typically occurs at elevated temperatures.The reaction temperature is typically from about 110° C. to about 160°C., more typically from about 130° C. to about 150° C. Thepolyol-epoxide reaction mixture may also be agitated and nitrogensparged. Generally, nitrogen sparging is the process of bubbling gaseousnitrogen through a liquid reaction. Nitrogen sparging replaces theamount of air initially present and thus, acts to reduce contact withwater present in the air initially entrained in polyols derived fromvegetable oils.

Lower acid vegetable oil-derived polyols produced using the method ofthis embodiment of the present invention typically have decreased watercontent as compared to other polyols produced from blowing soybean oil.It is presently believed that the decreased water content is due to theepoxide reactivity with water in the polyol-epoxide reaction used toproduce lower acid vegetable oil-derived polyols. Generally, the epoxidemay react with an acid, thereby reducing the residual acid in polyolsderived from vegetable oils, or with an alcohol (OH). The OH can comefrom the polyol or from water. Accordingly, the epoxide reacts with thewater to decrease the water content in the polyol derived from vegetableoil, typically soybean oil. Typically, a maximum water content of 0.10can be reduced by about 20% to about 30% to a water content of about0.07 to about 0.08.

Using the methods of this embodiment of the present invention, the acidvalue of a polyol derived from soybean oil decreases from initial valuesof from about 5.4 milligrams KOH/gram polyol to about 7.4 milligramsKOH/gram polyol to values from about 1.0 milligram KOH/gram polyol toabout 3.0 milligrams KOH/gram polyol. Polyol-epoxide reaction timetypically ranges from about 15 minutes to about 40 hours, more typicallyfrom about 30 minutes to about 2 hours. The polyol-epoxide reaction timeis a digestion process time and does not include the reaction timerequired to create the vegetable oil-derived polyol, typically a blownsoybean oil polyol or other blown vegetable oil polyol, or thevegetable-oil derived polyol produced by the oxidation process describedherein.

Preparation of Urethane Products Using Novel Polyols Derived from aVegetable Oil

Lower acid value polyols derived from vegetable oil, most typicallypolyols derived from blown soybean oil made in accordance with themethod discussed above, may be used to prepare any urethane product. Thelower acid polyols of the present invention may even be used to replacesome or all of the petroleum-based polyols, for example, in reactioninjection molding processes and the other processes discussed herein.The lower acid polyols of one embodiment of the present invention may beone of the components of the B-side in urethane reactions generally,which are reacted with an A-side that typically includes a prepolymer (atraditional petroleum-derived prepolymer or a prepolymer incorporating apolyol at least partially derived from a vegetable oil, such asdescribed in U.S. Pat. Nos. 6,624,244; 6,864,296; 6,881,763; and6,867,239, which are hereby incorporated by reference in theirentireties and, including a lower acid vegetable oil-derived polyol)and/or an isocyanate to form a polyurethane product.

Polyurethanes can be prepared in a one-step or a two-step process. Inthe one-step process, an A-side reactant is combined with a B-sidereactant. The A-side typically includes an isocyanate or a mixture ofisocyanates or prepolymer or mixtures of prepolymers and isocyanates.The A-side isocyanate reactant of the urethane is preferably comprisedof an isocyanate chosen from a number of suitable isocyanates as aregenerally known in the art. Different isocyanates may be selected tocreate different properties in the final product. The A-side reactant ofthe urethane typically includes one or more of the followingdiisocyanates: 4,4′-diphenylmethane diisocyanate; 2,4-diphenylmethanediisocyanate; and modified diphenylmethane diisocyanate. Typically, amodified diphenylmethane diisocyanate is used. Mixtures of differentisocyanates may also be used.

The A-side of the reaction may also be a prepolymer isocyanate alone orin combination with an isocyanate. The prepolymer isocyanate istypically the reaction product of an isocyanate component, preferably adiisocyanate, and most preferably some form of diphenylmethanediisocyanate, and a polyol component. The polyol component may bederived from a petroleum oil (such as polyether and/or polyesterpolyols), vegetable oil or a combination of petroleum and vegetableoil-derived polyols. Applicants have surprisingly discovered that lesspetroleum oil-derived polyol can be used when the vegetable oil-derivedpolyol is a lower acid vegetable oil-derived polyol. The polyol derivedfrom vegetable oil may be based upon blown or unblown soybean oil,rapeseed oil, cottonseed oil, palm oil, any other vegetable oildiscussed herein, or any other vegetable oil having a suitable number ofreactive sites. The most preferred vegetable oil used to derive thepolyol is soybean oil, in particular, a refined and bleached soybeanoil. There will still be unreacted isocyanate groups in the prepolymer.However, the total amount by weight of reactive A-side material hasincreased through this process. The prepolymer reaction reduces the costof the A-side component by decreasing the amount of isocyanate requiredand utilizes a greater amount of inexpensive, environmentally friendlypolyol derived from vegetable oil, preferably soybean oil. In order topermit the prepolymer diisocyanate A-side to react with the B-side,additional isocyanate typically must be added to elevate the isocyanatelevel to an acceptable level.

The A-side of one embodiment of the present invention may optionallyinclude an isocyanate (a first isocyanate) and a prepolymer comprisingthe reaction product of a second isocyanate and a first polyol at leastpartially derived from a vegetable oil, or a combination of variousisocyanates and prepolymers. Any suitable isocyanate may be used for thepurposes of the present invention. One polyisocyanate componentparticularly suitable for use in the reaction system of the presentinvention is RUBINATE® M. RUBINATE® M is an MDI (methylenebisdiphenyldiisocyanate), which is commercially available from Huntsman Chemicalsof Salt Lake City, Utah.

The B-side material is generally a solution of at least one polyol suchas in one embodiment of the present invention, the lower acid oxidizedsoybean oil polyol described above a cross-linking agent and/or a chainextender, and optionally a catalyst. If preparing a polyurethane foam, ablowing agent using a chemical or physical blowing agent is typicallyalso used. When a catalyst is added to the B-side, it is added tocontrol reaction speed and affect final product qualities.

Polyurethane elastomers and urethane foams can be prepared using loweracid vegetable oil-derived polyols in the B-side preparation alone or inthe presence of a multi-functional alcohol, cross-linking agent, orchain extender. Alternatively, a blend of traditional petroleum-basedpolyol and lower acid vegetable oil-derived polyols may be used alone orin the presence of a multi-functional alcohol, cross-linking agent, orchain extender.

The B-side reactant of the urethane reaction in one embodiment of thepresent invention typically includes a vegetable oil-based polyol and amultifunctional, active hydrogen-containing compound, typically a chainextender and/or a cross-linking agent. Multifunctional alcohols arepossible active hydrogen-containing compounds. Typically, a catalyst isalso included in the B-side. Examples of catalysts that may be utilizedinclude tertiary amines such as DABCO 33-LV® comprised of 33%1,4-diaza-bicyclo-octane (triethylenediamine) and 67% dipropyleneglycol,a gel catalyst available from the Air Products Corporations ofAllentown, Pennsylvania; DABCO® BL-22, a tertiary amine available fromthe Air Products Corporation; POLYCAT® 41 trimerization catalyst(N,N′,N″-dimethylaminopropylhexahydrotriazine) available from the AirProducts Corporation; and Air Products DBU® (1,8 diazabicyclo [5.4.0]).These catalysts may also be used as Lewis base catalysts in thepolyol-epoxide reaction used to form lower acid vegetable oil-derivedpolyols. While the level of catalyst used in the process of lowering theresidual acid value of the polyol is typically in amounts sufficient toat least substantially lower the acid value of the polyol, an excessamount can also be utilized. Typically, the amount of Lewis basecatalyst to be used should be approximated such that the residual acidvalue of the polyol is reduced as far as possible while not utilizingsuch an amount of Lewis base catalyst that substantial excess remains.Accordingly, while excess Lewis base material may be utilized, an excessof catalyst is generally not preferred because the presence of too muchcatalyst may begin to affect the color, odor, and viscosity of the loweracid vegetable oil-derived polyol used to produce urethane.

A blowing agent is typically included in the B-side of the reaction ofone embodiment of the present invention when preparing a urethane foammaterial or similar product. Blowing agents useful in the presentinvention include both chemical and physical blowing agents such as air,water, 134 A refrigerant available from Dow Chemical Co. of Midland,Mich., methyl isobutyl ketone (MIBK), acetone, methylene chloride, ahydroflurocarbon (HFC), a hydrochloroflurocarbon (HCFC), cycloaliphatichydrocarbons such as cyclopentane, an aliphatic hydrocarbon such asnormal or isopentane, or mixtures thereof. For carpet applications, air,sometimes referred to in the carpet industry as frothing, or water arethe presently preferred blowing agents. The concentrations of otherreactants may be adjusted to accommodate the specific blowing agent andthe desired end properties of the reaction product. These blowing agentscreate gas bubbles in the reacting mass.

Cross-linking agents and chain extenders used in the B-side reactant ofthe urethane reaction are at least difunctional (typically at least adiol). Typical cross-linking agents and chain extenders include ethyleneglycol and 1,4-butanediol; however, other diols or higher functionalalcohols such as glycerin may be used.

When preparing a urethane foam using lower acid vegetable oil-derivedpolyols, the B-side reactant may optionally further comprise a siliconesurfactant, which functions to influence liquid surface tension andthereby influence the size and stability of the bubbles that are formedand ultimately the size of the hardened void cells in the final foamproduct. This results in more uniform foam density, increased rebound,and a softer foam. Also, the surfactant may function as a cell openingagent to cause larger cells to be formed in the foam.

The use of vegetable oil-derived polyols, including lower acid vegetableoil-derived polyols, to prepare polyurethane products, includingelastomers and foams, realizes a significant cost savings because someor all of the more costly petroleum-based polyols may be replaced whenforming urethane products by any known method. Vegetable oils areabundant, renewable, and easily processed commodities, as opposed topetroleum-based polyols which entail significant associated processingcosts. There is a distinct marketing advantage to marketing productsthat are based on environmentally friendly, renewable resources such asvegetable oils.

Lower acid value polyols derived from vegetable oil, most typicallypolyols derived from soybean oil, made in accordance with one embodimentof the present invention increase available end uses and improve theperformance of polyols within current end uses. For example, the loweracid, higher functionality polyols can be used to produce rigidpolyisocyanurate foams such as pour-in-place foams, discontinuous metalpanels, laminated boardstock and bunstock foams. As already noted, it isbelieved that the residual acid retards isocyanate activity in theformation of polyol-based polyurethanes by interfering with theisocyanate/hydroxyl reaction to form urethane, urea, and/or isocyanuratepolymers. Also, it is believed that residual acid retards isocyanatereactivity by neutralizing the catalyst. Accordingly, the improvement inperformance is a direct result of the decreased residual acid content ofthe polyol and results in faster reactivities and/or lower polyurethanecatalyst requirements in formulations using polyols derived from blownvegetable oils, typically polyols derived from blown soybean oil. It ispresently believed that improvements in physical properties dependentupon flow, adhesion to surfaces, wet out, or processing of polyurethaneformulations containing such polyols derived from vegetable oil willalso occur. It is expected that using the lower acid vegetableoil-derived polyols of one embodiment of the present invention will alsoimprove the K-factor, a measurement of the thermal conductivity for aunit thickness of material. Also, use of polyols derived from vegetableoil in polyurethane formulations will result in improved densitydistribution and consistent spherical cell size across the material endproduct, creating enhanced dimensional stability.

As briefly discussed above, the higher functionality polyols of oneembodiment of the present invention which are derived from vegetable oilthat has been reacted with an oxidizing agent in the presence of TAML®catalyst are especially useful in a polyurethane pultrusion processbecause the higher acid value lowers the reaction rate of the urethane,a property which is very helpful in processing pultrusion applications.

The polyol at least partially derived from a vegetable oil of the B-sidein one embodiment of the present invention is typically blown vegetableoil, most typically blown soybean oil, blown rapeseed oil, blowncottonseed oil, blown safflower oil, blown palm oil, or blown canolaoil. Specific polyols derived from vegetable oil that may be utilizedinclude SOYOL™ P38N and SOYOL™ R2-052 polyols, both available fromUrethane Soy Systems Company of Volga, S. Dak. These polyols are nominaltwo functional polyols made from unmodified soybean oil and have ahydroxyl value of 52 to 56 mg KOH/gram polyol, typically 54 mg KOH/grampolyol, an acid value of 5.4 to 7.4 mg KOH/gram polyol, typically 6.4 mgKOH/gram polyol, a viscosity of 2500 cPs to 4000 cPs, typically 3000cPs, and a moisture content of less than 0.10 weight percent. Anotherexample is SOYOL™ R3-170 polyol, which is also available from UrethaneSoy Systems Company, and which is a nominal three functional polyol madefrom unmodified soybean oil and having a hydroxyl value of 160 mgKOH/gram to 180 mg KOH/gram, typically 170 mg KOH/gram, an acid value of5.0 mg KOH/gram to 7.3 mg KOH/gram, a viscosity of 3000 cPs to 6000 cPsat 25° C., and a moisture content of less than 0.10 weight percent.SOYOL™ R2-052C polyol is a polyol derived from soybean oil that exhibitsa low viscosity, typically measuring 800 cPs to 1200 cPs at 25° C. onthe viscometer.

The polyol(s) at least partially derived from vegetable oil may beutilized in place of some or all of the polyols derived from petroleumin pultrusion systems, thus providing a renewable resource in the finalpolymer composite. The polyol at least partially derived from vegetableoil, as discussed above, is typically a blown vegetable oil which can befurther modified by other processes. It has been surprisingly discoveredthat the process of blowing soybean oil causes formation of fatty acids.Typically, acids are undesirable in a polyol component to be used in theformation of urethane materials because the acid components interfereand, as a result, slow the urethane reaction rate and thereby affect theformation of the final urethane material. However, slower reaction ratesare desired in the case of continuous processes using snap-cure urethanechemistry because it significantly improves processing and thus providesthe ability to pultrude the material at a faster rate than conventionalurethane pultruded materials.

The B-side of the present invention may optionally further include apolyol derived from petroleum or other polyol. An example of twoparticularly preferred polyether polyols for use in the presentinvention are the propylene oxide adducts of glycerol, commerciallyavailable as JEFFOL® G30-650 and JEFFOL® G30-240 polyols. JEFFOL®G30-650 is a propoxylated glycerol with a hydroxyl value of about 650 mgKOH/gram available from Huntsman Petrochemical Corporation of Salt LakeCity, Utah and JEFFOL® G30-240 is a propoxylated glycerol with ahydroxyl value of about 240 mg KOH/gram, also available from Huntsman.

The B-side of one embodiment of the present invention may optionallyfurther include a second polyol derived from petroleum such as a sucrosebased polyether polyol. One such polyether is MULTRANOL® 9171, which isa sucrose based polyether polyol with a molecular weight of about 1,020.The MULTRANOL® 9171 has a hydroxyl number range of from about 330 mgKOH/gram to about 350 mg KOH/gram, a water content of less than 0.10weight percent, an acid number of less than 0.10 mg KOH/gram (max.), anda viscosity range of from about 7,000 cPs to about 11,000 cPs at 25° C.MULTRANOL® 9171 is typically a clear or amber viscous liquid which isslightly hygroscopic and may absorb water. MULTRANOL® 9171 iscommercially available from Bayer Corporation, Polymers Division,located at 100 Bayer Road, Pittsburgh, Pa.

The B-side of one embodiment of the present invention may optionallyfurther include an adhesion promoter, a coupling agent, or a blendthereof. One such adhesion promotor that may be used as a component ofthe B-side is SILQUEST® A-187 a Gamma-Clycidoxypropyl. SILQUEST®A-187 iscommercially available from GE Silicones of Wilton, Connecticut. Otherexamples of suitable adhesion promoters include amino alkoxy silanes andvinyl alkoxy silanes.

The B-side of one embodiment of the present invention may optionallyfurther include an adhesion promoter, a coupling agent, or a blendthereof. One such adhesion promotor that may be used as a component ofthe B-side is SILQUEST® A-187 a Gamma-Glycidoxypropyltrimethoxysilane.SILQUEST® A-187 is commercially available from GE Silicones of Wilton,Connecticut. Other examples of suitable adhesion promoters include aminoalkoxy silanes and vinyl alkoxy silanes.

The B-side of one embodiment of the present invention may optionallyfurther include a catalyst or a mixture of catalysts. A catalyst istypically used to increase the reaction rate of the polyol-isocyanateresin, or control the reaction order between competing reactions. Anorganometallic catalyst that may be utilized is K-KAT® 5218, which isused as an accelerator in the production of composite parts. The K-KAT®5218 catalytic activity accelerates the reaction of aromatic isocyanatesand alcohols. K-KAT® 5218 presents an alternative to conventional tincatalysts and can provide unique variations in cure response. K-KAT®5218 is commercially available from King Industries Inc. of Norwalk,Conn. Other suitable catalysts for use in the present invention includetin catalysts, typically organo tin catalysts; dialkyl tin salts ofcarboxylic acids; organo titanium catalyst; and mixtures thereof.

The B-side of one embodiment of the present invention may optionallyfurther include a chain extender suitable to extrapolate in a linearfashion due to terminal primary hydroxyl groups. One such chain extendersuitable for use in the present invention is 1,4-Butanediol (1,4 BDO).1,4 BDO is a versatile chemical intermediate because of its terminalprimary hydroxyl groups and its hydrophobic and chemical resistantnature. General characteristics of 1,4 BDO include a boiling point (@760TORR) of 228° C. (442° F.), a freezing point of 19° C. to 20° C., and ahydroxyl value of 1245 mg KOH/gram. 1,4-BDO is available from LyondellChemical Company of 1221 McKinney St., Houston Tex. Other suitable chainextenders that may be utilized as components of the B-side includedialkyl substituted methylene dianiline, diethyltoluene diamine,substituted toluene diamines, ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, and mixtures thereof.

The B-side of one embodiment of the present invention may optionallyfurther include a multifunctional alcohol and a cross linking agent. Forthe purposes of this application, a cross linking agent is a triol orhigher functional polyol that controls the flexibility, rigidity, andother physical characteristics of the final polymer composite. Amultifunctional alcohol suitable for use in the present invention isglycerin or sucrose.

The B-side of one embodiment of the present invention may optionallyfurther include a mold release compound such as an organophosphateester. Such a compound promotes internal mold release (IMR) of the finalpolymer composite. TECH-LUBE™ HP-200, available from Technick Productsof Rahway, N.J., is a suitable organophosphate ester which may be usedas a mold release agent in the present invention. The mold releasecompound, typically an organophosphate, helps the cured pultrudedproduct release from the heated die without damaging the composite withadhesion to the mold.

The B-side of one embodiment of the present invention may optionallyfurther include a molecular sieve, which functions to seek and eliminatemoisture. A preferred molecular sieve for use in the present inventionis BAYLITH® L-paste, which serves as a water scavenger. The paste canuse castor oil as a carrier. BAYLITH® L-paste is commercially availablefrom Bayer Corporation, located at 100 Bayer Road, Pittsburgh, Pa.BAYLITH® is commonly referred to as Zeolite.

The urethane material may be the reaction product of an A-side and aB-side where the A-side includes a compound having isocyanate reactivegroups, such as a methylenebisdiphenyl diisocyanate, and the B-sideincludes a vegetable oil-derived polyol, typically a soybeanoil-derived, oil polyol such as a blown soybean oil polyol; apetroleum-derived polyol; a castor oil; optionally, a chain extender; amultifunctional alcohol, such as a cross-linking agent; optionally, amold release compound; optionally, a molecular sieve; optionally, acoupling agent; and optionally, an organometallic catalyst. Theorganometallic catalyst is typically an organometallic oxidationcatalyst such as a tetra amido macrocytic ligand catalyst, mosttypically an iron tetra amido macrocylic ligand catalyst. The B-side mayinclude any of the following specific combinations:

B-side list #1

-   -   about 26% by weight of a combination of two vegetable (soybean)        oil-derived polyols;    -   about 35% by weight polyether polyol;    -   about 23% by weight castor oil;    -   about 5% by weight chain extender;    -   about 5% by weight multifunctional alcohol (cross-link agent);    -   about 3% by weight mold release compound;    -   about 2% by weight molecular sieve;    -   about 1% by weight coupling agent; and    -   about 0.4% by weight organometallic oxidation catalyst.

B-side list #2

-   -   about 26% by weight blown soybean oil polyol;    -   about 35% by weight propaxylated glycerol;    -   about 23% by weight castor oil;    -   about 5% by weight 1,4-butanediol;    -   about 5% by weight glycerin;    -   about 3% by weight organophosphate ester;    -   about 2% by weight zeolite;    -   about 1% by weight silane; and    -   about 0.4% by weight organometallic oxidation catalyst.

B-side list #3

-   -   about 25% by weight vegetable oil-derived polyol;    -   about 35% by weight polyether polyol;    -   about 26% by weight castor oil;

about 10% by weight multifunctional alcohol;

-   -   about 2% by weight molecular sieve;    -   about 1% by weight coupling agent; and    -   about 0.6% by weight organometallic oxidation catalyst.

B-side list #4

-   -   about 25% by weight blown soybean oil polyol;    -   about 35% by weight propoxylated glycerol;    -   about 26% by weight castor oil;    -   about 10% by weight glycerin;    -   about 2% by weight zeolite;    -   about 1% by weight silane; and    -   about 0.6% by weight organometallic oxidation catalyst.

B-side list #5

-   -   about 26% by weight vegetable (soybean) oil-derived polyol;    -   about 25% by weight polyether polyol;    -   about 26% by weight castor oil;    -   about 5% by weight multifunctional alcohol (cross-linked agent);    -   about 2% by weight molecular sieve;    -   about 1% by weight coupling agent; and    -   about 0.6% by weight organometallic oxidation catalyst,

B-side list #6

-   -   about 26% by weight blown soybean oil polyol;    -   about 26% by weight castor oil;    -   about 15% by weight propoxylated glycerol;    -   about 10% by weight polyether polyol;    -   about 5% by weight glycerin;    -   about 2% by weight zeolite;    -   about 1% by weight saline; and    -   about 0.6% by weight organometallic oxidation catalyst

Example I is one aspect of the present invention that comprises aformulation of:

EXAMPLE I

B-side:

Component Percent by weight Blown soybean oil polyol (SOYOL ™ R2-052) 10Blown soybean oil polyol (SOYOL ™ R3-170 16 Propoxylated glycerol(JEFFOL ® G30-650) 35 Castor oil 23 Adhesion Promotor (SILQUEST ® A-187)1 Organometallic catalyst (K-KAT ® 5218) 0.4 Chain extender (1,4 BDO) 5Multifunctional alcohol (Glycerin) 5 Organophosphate ester (TECHLUBE ®HP-200) 3 Molecular sieve (BAYLITH ® L-paste) 2 TOTAL: 100.4

A-side:

Component

Specialty isocyanate (RUBINATE® M)

Example II is another aspect of the present invention that comprises aformulation of:

EXAMPLE II

B-side:

Component Percent by weight Blown soybean oil polyol (SOYOL ™ P38N) 25Propoxylated glycerol (JEFFOL ® G30-650) 35 Castor oil 26 AdhesionPromotor (SILQUEST ® A-187) 1 Organometallic catalyst (K-KAT ® 5218) 0.6Multifunctional alcohol (Glycerin) 10 Molecular sieve (BAYLITH ®L-paste) 2 TOTAL: 99.6

A-side:

Component

Specialty isocyanate (RUBINATE® M)

Example III is another aspect of the present invention that comprises aformulation of:

EXAMPLE III

B-side:

Component Percent by weight Blown soybean oil polyol (SOYOL ™ R2-052C)26 Propoxylated glycerol (JEFFOL ® G30-240) 15 Polyether polyol(MULTRANOL ® 9171) 10 Castor oil 26 Adhesion Promotor (SILQUEST ® A-187)1 Organometallic catalyst (K-KAT ® 5218) 0.6 Multifunctional alcohol(Glycerin) 19 Molecular sieve (BAYLITH ® L-paste) 2 TOTAL: 99.6

A-side:

Component

Specialty isolyanate (RUBINATE® M 1.5:1

The above description is considered that of the preferred embodimentsonly. Modifications of the invention will occur to those skilled in theart and to those who make or use the invention. Therefore, it isunderstood that the embodiments described above are merely forillustrative purposes and not intended to limit the scope of theinvention, which is defined by the following claims as interpretedaccording to the principles of patent law, including the doctrine ofequivalents

The invention claimed is:
 1. A urethane material comprising the reactionproduct of an A-side and a B-side; wherein the A-side comprises at leastone isocyanate component; and wherein the B-side comprises an oxidizedvegetable oil polyol with an acid value of from about 1.0 mg KOH/grampolyol to about 3.0 KOH/gram polyol and having a hydroxyl value ofgreater than about 56 mg KOH/gram formed by reacting a vegetable oilwith an oxidizing compound in the presence of a tetra amido macrocyclicligand catalyst.
 2. The urethane material of claim 1, wherein the B-sidefurther comprises at least one or more other active hydrogen-containingcompounds; a catalyst; a blowing agent; a surfactant; an adhesionpromoter; a coupling agent; a mold release agent; and a molecular sieve.3. The urethane material of claim 2, wherein the at least one or moreother active hydrogen containing compound is chosen from the groupconsisting of a multi-functional alcohol, a cross-linking agent, and achain extender; wherein the multifunctional alcohol is at least onemultifunctional alcohol chosen from the group consisting of glycerin,sucrose, and mixtures thereof; wherein the crosslinking agent is a triolor higher functional polyol; and wherein the chain extender is a chainextender chosen from the group consisting of 1,4-butanediol, dialkylsubstituted methylene dianiline, diethyltoluene diamine, substitutedtoluene diamines, ethylene glycol, propylene glycol, diethylene glycol,dipropylene glycol, and mixtures thereof.
 4. The urethane material ofclaim 2, wherein the catalyst comprises a catalyst chosen from the groupconsisting of tertiary amines; dimethylethanolamine; triphenylphosphine;mono-, di- and tri- aliphatic and alkanol amines; pyridines;piperidines; aromatic amines; ammonia; ureas; quinolines; imidazoles;imidazolines; heterocyclic nitrogen compounds; organometallic catalysts;metal carbonyls; phosphine or phosphite complexes; dialkyl tin salts ofcarboxylic acids; and mixtures thereof; the blowing agent comprises ablowing agent chosen from the group consisting of air, water, a methylisobutyl ketone, acetone, methylene chloride, an aliphatic hydrocarbon,a hydroflurocarbon, a hydrochloroflurocarbon, and mixtures thereof; thesurfactant comprises a silicone surfactant; the adhesion promotercomprises an adhesion promoter chosen from the group consisting of aminoalkoxy silanes, vinyl alkoxy silanes, and mixtures thereof; the moldrelease agent comprises an organophosphate ester; and the molecularsieve comprises a zeolite.
 5. The urethane material of claim 1, whereinthe A-side consists of a methylenebisdiphenyl diisocyanate.
 6. Theurethane material of claim 1, wherein the B-side further comprises apetroleum-derived polyol wherein the petroleum derived polyol is apetroleum derived polyol chosen from the group consisting of a propyleneoxide adduct of glycerol, a polyether polyol, a polyester polyol, ormixtures thereof; and the B-side further comprises a castor oil.
 7. Theurethane material of claim 1, wherein the B-side further comprises acastor oil.
 8. The urethane material of claim 1, wherein the B-sidecomprises at least two oxidized vegetable oil polyols with an acid valueof from about 1.0 mg KOH/gram polyol to about 3.0 mg KOH/gram polyol. 9.The urethane material of 1, wherein the B-side further comprises a blownvegetable oil that is not the at least one oxidized vegetable oil polyolwherein the blown vegetable oil, when blown, has an increased hydroxylfunctionality as compared to the same vegetable oil that has not beenblown.
 10. A urethane material comprising the reaction product of anA-side comprising a compound having isocyanate functional groups and aB-side comprising at least one soybean oil-derived polyol having an acidvalue of from about 1.0 mg KOH/gram polyol to about 3.0 mg KOH/grampolyol; a petroleum-derived polyol; a castor oil; a chain extender; across-linking agent; a mold release compound; a molecular sieve; and anorganometallic catalyst.
 11. The urethane material of claim 10, whereinthe compound having isocyanate functional groups comprises amethylenebisdiphenyl diisocyanate, the organometallic catalyst comprisesan organometallic oxidation catalyst, and the B-side comprises: about26% by weight of a combination of two soybean oil-derived polyols; about35% by weight polyether polyol; about 23% by weight castor oil; about 5%by weight chain extender; about 5% by weight cross-linking agent; about3% by weight mold release compound; about 2% by weight molecular sieve;and about 0.4% by weight organometallic oxidation catalyst.
 12. Theurethane material of claim 10, wherein at least one soybean oil derivedpolyol is a blown soybean oil polyol with a reduced acid value of fromabout 1.0 KOH/gram polyol to about 3.0 KOH/gram polyol and wherein theB-side comprises: about 26% by weight blown soybean oil polyol; about35% by weight propoxylated glycerol; about 23% by weight castor oil;about 5% by weight 1, 4-butanediol; about 5% by weight glycerin; about3% by weight organophosphate ester; about 2% by weight zeolite; andabout 0.4% by weight organometallic oxidation catalyst.
 13. A urethanematerial comprising the reaction product of an A-side comprising acompound having isocyanate functional groups and a B-side comprising afirst polyol component chosen from the group consisting of at least onesoybean oil-derived polyol having an acid value of from about 1.0 mgKOH/gram polyol to about 3.0 mg KOH/gram polyol; a second polyolcomponent consisting of at least one petroleum-derived polyol; a thirdpolyol component consisting of castor oil; a fourth polyol componentconsisting of multifunctional alcohol; a molecular sieve; and anorganometallic catalyst.
 14. The urethane material of claim 13, whereinthe compound having isocyanate functional groups comprisesmethylenebisdiphenyl diisocyanate and the organometallic catalystcomprises an organometallic oxidation catalyst and the B-side comprises:about 25% by weight of the first polyol component; about 35% by weightof the second polyol component and the second polyol component is apolyether polyol; about 26% by weight of the third polyol component;about 10% by weight of the fourth polyol component and themultifunctional alcohol is a cross-linking agent; about 2% by weightmolecular sieve; and about 0.6% by weight organometallic oxidationcatalyst.
 15. The urethane material of claim 13, wherein the firstpolyol component is a blown soybean oil polyol with a reduced acid valueof from about 1.0 KOH/gram polyol to about 3.0 mg KOH/gram polyol andwherein the B-side comprises: about 25% by weight of the first polyolcomponent; about 35% by weight of the second polyol component and thesecond polyol component is a propoxylated glycerol; about 26% by weightof the third polyol component; about 10% by weight of the fourth polyolcomponent and wherein the fourth polyol component is glycerin; about 2%by weight zeolite; and about 0.6% by weight organometallic oxidationcatalyst.
 16. The urethane material of claim 13, wherein the compoundhaving isocyanate functional groups comprises methylenebisdiphenyldiisocyanate, the organometallic catalyst comprises an organometallicoxidation catalyst, and the B-side comprises: about 26% by weight of thefirst polyol component wherein the first polyol component is a singlesoybean oil-derived polyol; about 25% by weight of the second polyolcomponent and the second polyol component is a polyether polyol; about26% by weight of the third polyol component; about 5% by weight of thefourth polyol component and wherein the fourth polyol component is across-linking agent; about 2% by weight molecular sieve; and about 0.6%by weight organometallic oxidation catalyst.